Inhibiting storage tank corrosion



y 6, 1953 A. c. BROYLES 2,639,971

INHIBITING STQRAGE TANK CORROSION Filed Jan. 29, 1949 I 2 Sheets-Sheet l GAUGE HATCH CZZU'LIQ c.bnogls Sin-v erzbor 15 110. (9. 7 W abbobrz as M y 953 A. c. BROYLES 2,639371 INHIBITING STORAGE TANK CORROSION Filed Jan. 29, 1949 2 Sheets-Sheet 2 On. LEVEL.

Cilun'rz C. broglcs 1 Unvenbor br g Clbborneg Patented May 26, 1953 INHIBITING STORAGE TANK CORROSION Alvin C. Broyles, Tulsa, Okla., assignor to Standard Oil Development Company, a corporation of Delaware Application January 29, 1949, Serial No. 73,647

Claims.

The present invention is directed to a method for reducing or minimizing corrosion in vessels containing material which evolves corrosive acidic vapors. The invention relates especially to a novel class of inhibitor compounds which may be added to the vapor space of metal storage tanks to prevent corrosion of the tank. More particularly, the invention is directed to the prevention of corrosive action in the vapor space of metal tanks used for the storing of sour crude petroleum oils. In accordance with the present invention a low concentration of a volatile nitroparaflin is maintained in the vapor space of the tank to be protected.

At the present time in the chemical and related industries it is becoming increasingly important to decrease corrosion losses. A pronounced effort is being made to determine ways in which equipment of all types may be protected against deterioration due to corrosion. In the oil industry in particular it is anticipated that very substantial economic savings may be made in this field. An especially troublesome type of corrosion is that encountered in storage tanks and vessels wherein sour crude petroleum is held for considerable periods of time. In general sufiicient acidic vapors, particularly hydrogen sulfide, are evolved by sour crude oil so as to establish in conjunction with oxygen and water vapor contained in the tanks a sufficiently corrosive atmosphere to cause serious damage to the tank, particularly to that portion which encloses the vapor space above the stored liquid and thereby severely limit the life of the tanks.

It has been noted that when sour crude oil is stored in a tank, the vapor in the space above the liquid level will ordinarily contain hydrogen sulfide in volume concentrations lying within the average range of from about 0.2 per cent to about 8 per cent. Normally, the maximum hydrogen sulfide concentration will be about 2 or 3 per cent. During normal operation of the tank, that is during filling and emptying or even during a period when no oil is added to or removed from the tank, air and water vapor will find its way into the vapor space above the liquid. Hydrogen sulfide in the presence of droplets of condensed moisture and particularly in the added presence of air or oxygen is extremely corrosive to the metal surface of the tank and can cause a considerable loss of metal from the inside of the tank in a relatively short period of time.

Extensive study of the problem of corrosion by hydrogen sulfide and similar sulfur-containing gases has revealed that hydrogen sulfide is relatively non-corrosive to metal surfaces even when moisture is present, provided no air or oxygen is present. On the introduction of air or oxygen, however, corrosion rates-rise rapidly, and serious corrosion can occur with an oxygen concentration as low as 2% in the presence of hydrogen sulfide.

It has further been noted that an increase in the per cent oxygen concentration has a much greater effect on the corrosion rate for a given hydrogen sulfide concentration than does a similar increase in the per cent of hydrogen sulfide for a given concentration of oxygen. A very severe corrosive condition occurs when 15 to 20 volume per cent oxygen is present and when the hydrogen sulfide concentration is as low as 0.2 per cent. In general it has been found in field operations that when the oxygen concentration is relatively high the hydrogen sulfide concentration will be fairly low so that when the vapor space of a tank contains oxygen in the volume per cent range of about 15 to 20, the hydrogen sulfide concentration will be no higher than 2 or 3 per cent.

The presence of such high oxygen concentrations can readily occur in a storage tank that has not been tightly sealed so that air has more or less free access to the inside of the tank. When the tank has been exposed to the sun or to high atmospheric temperatures during the daytime and then cools ofi during the night, .breathing occurs and moist air is drawn into the tank. If the temperature falls below the dew point, droplets of moisture form on the exposed internal surface of the tank and subsequent corrosion occurs as a result of the combined action of this moisture and hydrogen sulfide and oxygen present in the vapor space.

Attempts have previously been made to reduce this corrosion by coating the inside surface of such storage tanks with various protective materials, but this procedure has not proved very successful for various reasons, including insufficient adhesiveness of the coating to the tank surface, solvent action of the stored liquid on the coating, breaks or discontinuities in the coating, prohibitive cost and the like.

It is an object of the present invention to provide an emcient process for reducing or preventing corrosion in the vapor space of storage tanks containing liquids which evolve corrosive vapors. Other and further objects of the present invention will be apparent from the ensuing description and from the accompanying drawings in which Figs. 1 and 3 represent a crosssectional view of conventional storage tanks containing suitable devices for operation of the present invention, and in which Fig. 2 depicts one suitable form of container for introducing corrosion preventing agents into a storage tank.

In accordance with the present invention it has now been found that corrosion can be reduced or prevented by injecting or otherwise introducing relatively :small quantities of a nitroparafiin into the vapor space of the tank. The process is attractive since an extremely low concentration of nitroparaffin is required.and..since..it,appears that a definite protectivefilm' is placed on the surface of the tanksthusaelengthening the life of the protection achieved.

The discovery on which this invention is based is that volatile nitroparaffinsin. some,.manner not entirely understood are effective to prevent substantially corrosion of the type indicated. While it is contemplated that higher boiling nitroparamns would alsm-be-suitable for. this purpose it is .preferreduto employ those nitro- -paraffins which .by :their nature are-sufficiently volatile to form a protectiveiatmosphere-at the temperature at which storage .tanks-.are-norma1- ly maintained. Consequently vthe preferredinhibitors of the present inventiomarei thesthrvee vlow boiling nitroparafiins .nitromethane, nitroethane, and nitropropane. Each=ofthese .compounds is sufiicientlyvolatilezso. as toprovide a suitable protective atmosphere in the -a storage tank or vessel. -In-accordance with this-invention corrosion 1 inhibition may; Joe-achieved using these compounds by. introducing into the. vapor :space of the tankto-baprotected-sufiicient nitrolparaffin to maintain a; concentration-pf; about 0.1; to :.about 0.5 volume-per cent. The-nitroparafiin, preferably nitromcthane may'be introduced into. the vapor .Space: by;v means of: one .or more spraying jets,..bl1ta aalmoreasatisfactory method-is toplaee the-nitroparaiiin inxa relatively shallow vessel I suspended 1 in? the vapor space. of the 'tanklxso thatqthe nitroparailin can be allowed to evaporate freely. In-order toiprotest the vaporspa-ce of a23001 barrelgstoragetank in actual service where; losses.=.oc cur' .athrough fbreathing and the like, it .uhas {2 been r'found necessary toprovide for, the evaporation of &from 150 to 450 ml. ;of nitromethane.perzdayeintogthe vapor space. i This can ibe .accomplished@ by; providing inside the tank a yesselzirrwhich.thenitromethane will, have. a .free surface; area: .oirrlOO .to v250 sq. inches. Nitromethanezcan be introduced into ,;the shallow evaporation wressel uthrou-gh the gaugehatch of .the,tankloraiitmaylloe introducedthrough axsmall: supply I line runningzinto :the vessel.

The 1 methods of introducing: nitromethaneior a related nitroparafiin into. a; storage .tankucan be .more clearly understoodfrom athe-accompanying drawings. .rF-ig. 1. representsv inwcrosssection, a conventionaloil storage ztank quipped with devices for .introducing: the: nitroparanin inhibitor. In. .thedigure, referenceunumeral. I designates a tank havinga welded: 1110012 2 .pro- .vided .with'v a .central..opening 3- having anhatch cover 4. The tankzhas= an-xinletnpipe and: a drawofi 1 line: .-(neither gone; shown) ,1 for filling and emptying. the::.tank. '.-Suspended:-from the roof 2. by. a suitable; bracket: .6, :is. asshallowutray or .nest of trays .9, Linwhich;may:.:bep1aced.ithe nitroparaffin inhibitor. .Thismaybe. introduced through :the .;hatchw ,-openi1n .Bracket" 6" :is pivotally attached to-.,the eroof atjnpoint so that the; bracket. and .the pansvcanabe w ng insupported by a wire support '2, having locks .adaptedto slideover bracket 6 shown in Fig. 1.

Other wire supports 8 suspend lower trays below the .top .tray.

Insteadof filling the evaporating pan through the hatchway of the tank it is also contemplated .to. accomplish this from the exterior of the tank .with a hinged cover 23.

as shown in Fig. 3. A pan it having suitable evaporating area is supported by suitable means such as brackets l6, attached to the roof of the tank. -A pipe orconduit'ec is fitted into-pan J9 at-a point at or near the bottom of ,the pan and 7 extends substantially horizontally through a suitable gasket or sealing means 2!, .to apoint on the outside of the tank where it communicates with aifilling andinspection chamber 22- fitted The latter is preferably providedwith a small'vent hole to ensure that the liquid levels inpan 19 and in chamber 22 will: beat the same-height. Chamber '22 .maybe welded or riveted to; the tank ormay v.be otherwise attached as by. suitable brackets and is preferably placedatabout the samelevel as pan 59. By placing thegbottom of chamber v22 at a slightly lower ,level than the bottom of .pan 1H9, line 20 connecting. .=the-bottoms.of the .two vessels will have-a slight-doWnward;,-pitch, thus .facilitating ,the removal .of inhibitor through -petcock .f 2 when desired. -Suitable reference marks..may: beqprovided in chamber 22 to indicate the levelof liquidin pan; Is and filling of the systemand inspection of the level can be made by lifting hinged cover; 23.

Laboratory tests demonstrating the efiiciency of -nitromethane. and related, nitroparaffins as inhibitors of corrosion in the vapor space of tanks containing corrosive atmospheres are 'described in-the examples-presented below. .In

determining the corrosion inhibition brought about by the. compounds. of this inventiona glass laboratory tank was employed having 1 an opening at the top. This opening wasgthen closed by asheet of mild steel held onkthe top by. awsealed ring closure, the assembledv tank :thus simulating an actual storage tank having 313119011" of Y mild-steel. Corrosive atmospheres as desiredtogether with inhibitors to be tested were then pumpedv into. this vessel through a suitable opening, and the tank was placed-outdoors so as to exposeit to temperature .changes iniorder to simulate actual storage tank conditions. It was found that close correlation exists between thistype of test andatestconducted With a full size storage tank. .The-atrnosphere -ernployedwas .onechosen to. correspond as .closelyas possible to the type of atmosphere-encounteredover. a sour crude oil in astorage tank and consisted. principally of natural 2 gas: containing from 2 to 15% oxygen, about 2 car .bon. dioxide and about 2% hydrogen sulfide. As stated the; vessels employed for the vtest were placed. in. an exposed. position outdoors ;.and the tests were run during atperiodi oflweatherwhen the a average? temperature produced within. i-the vessel was, .about...65 and; .varied between-.a

minimum of about 50 F. and a maximum of 1 changes in temperature closely corresponded to the situation in an actual storage tank. In each test run two or three vessels containing the same test atmosphere were employed so that the data presented herein represent an average value of several tests. In each case wherein an inhibitor was added to the particular atmosphere used similar control vessels were also employed corresponding identically in every particular except as to the presence of an inhibitor. The mild steel panel employed in the test was a panel which had been prepared by being freshly sandblasted, to present a clean surface, followed by washing in hot' distilled water and drying by contact with acetone and heating in an oven. The weight of the mild steel panel was carefully determined both before and after the tests run.

Example 1 As one example of the present invention an atmosphere comprising 2 hydrogen sulphide, 15% oxygen, 2% carbon dioxide and 81% natural gas was placed in a vessel of the type described. In a similar vessel containing the same atmosphere 0.012 gram of nitromethane .per 1800 milliliters of atmosphere was placed. During the test the stated concentration of nitromethane was added daily. At the end of three days it was found that in vessels into which nitro-methane had been introduced the steel panels showed a weight loss of 27.9 milligrams per sq. decimeter per day. In vessels containing the same atmosphere but without added nitromethane the panels showed a weight loss of 267.2 milligrams per sq. decimeter per day. On a percentage basis it can be concluded that there was or 89.6% retardation of corrosion.

Example 2 Example 3 As a further example of this invention similar tests were run employing nitropropane as the inhibitor. In this case 0.16 gram of nitropropane was employed for each 1800 milliliters of atmosphere. All other conditions of the test were as indicated above with the exception that the test period was 1 day rather than 3 days. The steel panels employed showed a weight loss without the inhibitor protection of 192.7 milligrams per sq. decimeter per day as against a weight loss of 44.7 milligrams per sq. decimeter per day in the case where the vessel contained the nitropropane. These data show a. corrosion retardation of 76.8

Example 4 In order to determine whether or not a definite protective film is in some. manner deposited on the surface of the tank to be protected, prolonged tests were run during which the corrosive atmosphere was frequently changed, but the inhibiting nitroparafiin employed was added only at the beginning of the test so that subsequent changes of the atmosphere substantially removed any free inhibitor vapors. For example, a 5 day test was made in which inhibitor was added only at the beginning of the test and in which the corrosive atmosphere was then changed on the third day of the test. The inhibitor employed was nitromethane and the concentration used was 0.012 gram per 1800 milliliters of atmosphere. It was found that at the end of 5 days the steel panel in the vessel which had been inhibited showed a weight loss of 8 milligrams per square decimeter per day while a control panel ina vessel in which no inhibitor was added showed a weight loss of 83.4 milligrams per square decimeter per day. These data gave a corrosion retardation figure of 90.4%. It will be noted by comparison of this test with the 3 day test reported in Example 1 that essentially the same corrosion inhibition was obtained, even though two days of the test were conducted substantially without the presence of any added nitromethane. It therefore appears that during the initial 3 days of the test a more or less permanent corrosion inhibition of the mild steel was attained so that on eliminating nitromethane from the system corrosion was in some manner still prevented. It is possible that a tightly adherent film is somehow deposited on the surface of the mild steel panel. It should be understood, however, that this invention is not to be limited by any theory of its mode of operation.

Example 5 In a further test which was conducted for a period of 7 days, the atmosphere was changed 4 times, the corrosion inhibitor being introduced only on the first day. Again nitromethane was employed as the inhibitor at a concentration of 0.012 gram per 1800 milliliters of atmosphere. After the first day of the test as indicated the atmosphere was completely changed, effectively eliminating substantially all of the free nitromethane from the system. This procedure was repeated 3 times during the test, namely on the 4th, 5th, and 6th days. Controls were also run in which the identical procedure was carried out except that no nitromethane was added at any time to the vessels. At the end of 7 days it was found that the steel panel in the vessel which had contained inhibitor had lost 158 milligrams per sq. decimeter per day while the control steel panel had lost 465 milligrams per sq. decimeter per day. The corrosion retardation was therefore, 66.1%. While it is to be noted that the same degree of corrosion inhibition was not obtained as in the case where nitromethane is constantly maintained in the vessel nevertheless it is to be observed that the corrosion was substantially cut down. Again it appears certain from these data that a definite protective film was placed on the mild steel panel in the initial part of the test which was probably not entirely displaced even at the end of the test.

The effectiveness of the present invention is further illustrated by actual field tests that have been conducted on 300 barrel steel storage tanks. In these tests the storage tanks were maintained in normal operation for storing an Arkansas sour crude oil, which on analysis was found to contain from about 2 to about 4 cubic feet of evolvable 10f this size.

hydrogenrsulfidelper bar-rel. :jTest periods. were .maintained for. a rsufficient time to .averageout for asufiicientlylongperiod of timesothat the tanks .at somev time wouldbe :fullv .or nearly.-ful1 -..and at other;.times wouldz-bez-empty. 011-: the average ,eachtank was a1ternate1y:-.fi11ed;and .emptied in about 4- or 5 day'cycles. Threegtanks awereqemployed and in :the -vapor-.;space.ofieach.

tank; were placed;carefully.weighedsandblasted steel panels.

:The test panels=were .loolted to. the manhole cover. in the roof of 'thetankin ordenthat they \WOllld be given the fullest; opportunity to accumulatecondensed moisture in the samemanner; as the; walls and roof of the tank and thus besubjected to the same corrosive conditions, 8.5917108 latter; surfaces. After LS- days of exposure-the .testpanels were again Weighed to determine con- -trol corrosion rates. Then weighed steel panels were again inserted in the tanks and nitromethane vapors, were introduced into the vapor space in ;each tank by placing liquid nitromethanein shalqlowpans suspended from the roof. of eachtank and allowing it .to evaporate. liters of-nitromethane evaporatedyineach tank About 100 millieach day. The following results were obtained at .the end of:.10- d ays.

" Results'of Nitromethane Field Test TankNumber ControlCor- Corrosion Rate,

-rosion Rate, Mdd (Nitro- Percent Re- M dd(48 days methane Treated, tardation Exposure) days) The increase in per cent retardation from Tank 1 to Tank 3 may be-explained by the arrangement of the'vent lines: vapors leaving Tank 1 pass through-Tank 2, then through Tank 3 to the atmosphere.

The results show that appreciableretardation of corrosion may be obtainedby introducing: 100 milliliters of nitromethane per dayinto the vapor space of a 300 barrel storage tank containingsour crude oil and that the corrosion inhibition improves as the concentrationof nitromethane :is raised. above :that figure.

Depending on the particular conditions encountered, fromabout. 150 to about 450. millilitersvof nitromethane per day will protecta storage tank about 0.7 lb. .of .nitromethane. per dayaper 1000 ,cubic feet of storage capacity.

Other field tests; revealed that 95;.to,.99%.-retardation of corrosion could. be effected byrpmaintaming a concentration of 0 .2 t0 0.4 volume:per-- This is equivalentxtoaabout 02.1120

pai--.ticularly-. in thewapor space thereofibymain- ..taihinghn'. :the .vapor: space EL: concentration of .gabout 0.2 1b. to. about flfi' lbiof, a volatile nitroparafiin-per ;10.00.c11bic .feet of storagecapacity; Efiec- :;=ti.ve corrosion protection can likewisebe obtained by maintaining a.-..concentration: of;0.1 to 0.5 vol- ;.-ume;percent;andpreferably (1.2 to 0.4 volume. perecentof the mtroparafiinin the vaporspace. The .wolatile nitroparafiinis preferably selected from the class-ccnsisting of nitromethane ,nitroethane andmnitropronan nitromethane. vb in the i pre- -iierredinhibiton;;;Introducticn Ofthe .nitroparafiin -may1be; accomplished :inanygdesired manner; f or ;-examp1 ,z vess 1. conta nin liqu d :nitroparaifin and hav-in anzcp n ton 1w.- be susp nded n. th vapor s aceof thetank to be protected. Againif desired, the nitroparafiin-may bepositione'd inan :auXiI aIYNB scI uts d the .tanka its apo s -conducted from. this vessel into the, tank tosupply :20

the nitIIOparaifin atmosphere. 7 The auxiliary yessel may or may not be heated isomewhat as desired to insure volatilization of the nitroparafiin. The essential requirement is that the vapor space .be supplied- .withnitroparaffin in; the concentration reported above.

-Whatqis claimed:

a l. A methodforminimizing corrosion in ametal vessel whichhas, a vaporspaceand carries a material evolving acidic Vaporshich comprises maintaining in said vapor space. a, volatile; nitroparaflin selected from the class consisting of nitromethane, -nitroethane,- and :nitropropane.

2. A- method for; minimizing; corrosion in metal storage, tank for-oil which evolves corrosive :sul- -phur.-ccntainin apors which? c mpr ses. maintamin in the; vapor space or aid. tanks a con- ..t ininga voitatile vni roparaiifin..s .e1ec.t.eci from the class con istin of mitromethane. .xnitroethane,

- an .nitrcprcnanea r t 02-0- 1 of .nitr n raffinv er .d nner cubic feet of stora e capacity frsaidtank LVINfC.,BRO-YLES. 

1. METHOD FOR MINIMIZING CORROSION IN A METAL VESSEL WHICH HAS A VAPOR SPACE AND CARRIES A MATERIAL EVOLVING ACIDIC VAPORS WHICH COMPRISES MAINTAINING IN SAID VAPOR SPARE A VOLATILE NITROPARAFFIN SELECTED FROM THE CLASS CONSISTING OF NITROMETHANE, NITROETHANE, AND NITROPROPANE. 